Environmental Science and Pollution Research

, Volume 26, Issue 1, pp 806–815 | Cite as

Highly dispersed core-shell iron nanoparticles decorating onto graphene nanosheets for superior Zn(II) wastewater treatment

  • Yihao Yao
  • Shiming Huang
  • Wen Zhou
  • Airong LiuEmail author
  • Weijia Zhao
  • Chenyu Song
  • Jing Liu
  • Weixian Zhang
Research Article


This study reports the preparation of highly dispersed nanoscale zerovalent iron (nZVI) with core-shell structure decorated onto graphene nanosheets (Gr-NS) to form nZVI-Gr-NS composite. Meanwhile, its excellent performance for concentrated Zn(II) wastewater treatment is also studied. The adsorption of Zn(II) onto nZVI-Gr-NS is well simulated by the pseudo-second-order model, which indicates the adsorption is the rate-controlling step. Moreover, the adsorption isotherms of Zn(II) on the nZVI-Gr-NS can fit well with the Langmuir model. The negative thermodynamic parameters (△GƟ, △HƟ, △SƟ) calculated from the temperature-dependent isotherms indicate that the sorption reaction of Zn(II) is an exothermic and spontaneous process. The high saturation magnetization (37.4 emu g−1) of the nZVI-Gr-NS makes separation of nZVI-Gr-NS-bound Zn(II) easily and quickly from aqueous solution. Most importantly, nZVI-Gr-NS composites not only remove Zn(II) but also spontaneously remove As, Se, and Cu ions from real smelting wastewater samples. This study provides a good solution for heavy metal removal in real wastewater.


Fabrication nZVI-Gr-NS Zn(II) Adsorption Smelting wastewater 



Financial support from the National Science Foundation of China (NSFC grants nos. 11475127, 41673096, 41772243, 51578396) is acknowledged.

Supplementary material

11356_2018_3631_MOESM1_ESM.docx (384 kb)
ESM 1 (DOCX 384 kb)


  1. Ali I (2012) New generation adsorbents for water treatment. Chem Rev 112:5073–5091CrossRefGoogle Scholar
  2. I. Ali and V. K. Gupta, Das, Advances in water treatment by adsorption technology, Nat Protoc, 2006, 1, 2661–2667Google Scholar
  3. Bhattacharya AK, Mandal SN, Das SK (2006) Adsorption of Zn(II) from aqueous solution by using different adsorbents. Chem Eng J 123:43–51CrossRefGoogle Scholar
  4. Chandra V, Park J, Chun Y, Lee JW, Hwang IC, Kim KS (2010) Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. ACS Nano 4:3979–3986CrossRefGoogle Scholar
  5. Chang H, Wu H (2013) Graphene-based nanocomposites: preparation, functionalization, and energy and environmental applications. Energy Environ Sci 6:3483–3507CrossRefGoogle Scholar
  6. Cheng G, Liu YL, Wang ZG, Zhang JL, Sun DH, Ni JZ (2012) The GO/rGO–Fe3O4 composites with good water-dispersibility and fast magnetic response for effective immobilization and enrichment of biomolecules. J Mater Chem 22:21998–22004CrossRefGoogle Scholar
  7. Cong HP, Ren XC, Wang P, Yu SH (2012) Macroscopic multifunctional graphene-based hydrogels and aerogels by a metal ion induced self-assembly process. ACS Nano 6:2693–2703CrossRefGoogle Scholar
  8. Cui L, Zhu JY, Meng XM, Yin HS, Pan XP, Ai SY (2012) Controlled chitosan coated Prussian blue nanoparticles with the mixture of graphene nanosheets and carbon nanospheres as a redox mediator for the electrochemical oxidation of nitrite. Sensor Actuat B-Chem 161:641–647CrossRefGoogle Scholar
  9. Ferrari AC, Robertson J (2000) Interpretation of Raman spectra of disordered and amorphous carbon. Phys Rev B 61:14095–14107CrossRefGoogle Scholar
  10. Geim AK, Novoselov KS (2007) The rise of graphene. Nat Mater 6:183–191CrossRefGoogle Scholar
  11. Gu C, Jia H, Li H, Teppen BJ, Boyd S (2010) Synthesis of highly reactive subnano-sized zero-valent iron using smectite clay templates. Environ. Sci. Technol. 44:4258–4263CrossRefGoogle Scholar
  12. Guo J, Wang R, Tjiu WW, Pan J, Liu T (2012) Synthesis of Fe nanoparticles@graphene composites for environmental applications. J Hazard Mater 225-226:63–73CrossRefGoogle Scholar
  13. Hoch LB, Mack EJ, Hydutsky BW, Hershman JM, Skluzacek JM, Mallouk TE (2008) Carbothermal synthesis of carbon-supported nanoscale zero-valent iron particles for the remediation of hexavalent chromium. Environ Sci Technol 42:2600–2605CrossRefGoogle Scholar
  14. Hummers WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339CrossRefGoogle Scholar
  15. Kalavathy H, Karthik B, Miranda LR (2010) Removal and recovery of Ni and Zn from aqueous solution using activated carbon from Hevea brasiliensis: batch and column studies. Colloid surf B: Biointerfaces 78:291–302CrossRefGoogle Scholar
  16. Kanel SR, Greneche JM, Choi H (2006) Arsenic(V) removal from groundwater using nano scale zero-valent iron as a colloidal reactive barrier material. Environ. Sci. Technol. 40:2045–2050CrossRefGoogle Scholar
  17. Kemp KG, Seema H, Saleh M, Le NH, Mahesh K, Chandra V, Kim KS (2013) Environmental applications using graphene composites: water remediation and gas adsorption. Nanoscale 5:49–71CrossRefGoogle Scholar
  18. Khin M, Nair AS, Babu VJ, Murugan R, Ramakrishna S (2012) A review on nanomaterials for environmental remediation. Energy Environ Sci 5:8075–8109CrossRefGoogle Scholar
  19. Kržišnik N, Mladenovič A, Škapin AS, Škrlep L, Ščančar J, Milačič R (2014) Nanoscale zero-valent iron for the removal of Zn2+, Zn(II)-edta and Zn(II)-citrate from aqueous solutions. Sci Total Environ 476-477:20–28CrossRefGoogle Scholar
  20. Li D, Muller MB, Gilje S, Kaner RB, Wallace GG (2008) Processable aqueous dispersions of graphene nanosheets. Nat Nanotechnol 3:101–105CrossRefGoogle Scholar
  21. Liu AR, Zhang W-X (2014) Fine structural features of nanoscale zero-valent iron characterized by spherical aberration corrected scanning transmission electron microscopy (Cs-STEM). Analyst 139:4512–4518CrossRefGoogle Scholar
  22. Liu AR, Liu J, Pan BC, Zhang W-X (2014a) Formation of lepidocrocite (γ-FeOOH) from oxidation of nanoscale zero-valent iron (nZVI) in oxygenated water. RSC Adv 4:57377–57382CrossRefGoogle Scholar
  23. Liu F, Yang J, Zuo J, Ma D, Gan L, Xie B, Wang P, Yang B (2014b) Graphene-supported nanoscale zero-valent iron: removal of phosphorus from aqueous solution and mechanistic study. J Environ Sci 26:1751–1762CrossRefGoogle Scholar
  24. Liu J, Liu A, Zhang W-X (2016) The influence of polyelectrolyte modification on nanoscale zero-valent iron (nZVI): aggregation, sedimentation, and reactivity with Ni(II) in water. Chem Engin J 303:268–274CrossRefGoogle Scholar
  25. Liu AR, Liu J, Zhang W-X (2017) Evolution of nanoscale zero-valent iron (nZVI) in water: microscopic and spectroscopic evidence on the formation of nano- and micro-structured iron oxides. J Hazard Mater 322:129–135CrossRefGoogle Scholar
  26. Lu C, Chiu H (2006) Adsorption of Zinc(II) from water with purified carbon nanotubes. Chem Engineer Sci 61:1138–1145CrossRefGoogle Scholar
  27. Lu C, Chiu H (2008) Chemical modification of multiwalled carbon nanotubes for sorption of Zn2+, from aqueous solution. Chem Engineer J 139:462–468CrossRefGoogle Scholar
  28. Manning BA, Hunt ML, Amrhein C, Yarmoff JA (2002) Arsenic(III) and arsenic(V) reactions with zerovalent iron corrosion products. Environ. Sci. Technol. 36:5455–5461CrossRefGoogle Scholar
  29. Meena AK, Mishra GK, Rai PK, Rajagopal C, Nagar PN (2005) Removal of heavy metal ions from aqueous solutions using carbon aerogel as an adsorbent. J Hazard Mater 122:161–170CrossRefGoogle Scholar
  30. Memmert U (1987) Bioaccumulation of zinc in two freshwater organisms (Daphnia magna, Crustacea and Brachydanio rerio, Pisces). Water Res 21:99–106CrossRefGoogle Scholar
  31. Mu JB, Shao CL, Guo ZC, Zhang MY, Zhang ZY, Zhang P, Chen B, Liu YC (2012) In2O3 nanocubes/carbon nanofibers heterostructures with high visible light photocatalytic activity. J Mater Chem 22:1786–1793Google Scholar
  32. Oren AH, Kaya A (2006) Factors affecting adsorption characteristics of Zn2+ on two natural zeolites. J Hazard Mater 131:59–65CrossRefGoogle Scholar
  33. Park S, Ruoff RS (2009) Chemical methods for the production of graphenes. Nat Nanotechnol 4:216–224CrossRefGoogle Scholar
  34. Ruparelia JP, Duttagupta SP, Chatterjee AK, Mukherji S (2008) Potential of carbon nanomaterials for removal of heavy metals from water. Desalination 232:145–156CrossRefGoogle Scholar
  35. Shi LN, Zhang X, Chen ZL (2011) Removal of chromium (VI) from wastewater using bentonite-supported nanoscale zero-valent iron. Water Res 45:886–892CrossRefGoogle Scholar
  36. Shi L-N, Zhou Y, Chen ZL, Megharaj M, Naidu R (2013) Simultaneous adsorption and degradation of Zn(2+) and Cu(2+) from wastewaters using nanoscale zero-valent iron impregnated with clays. Environ Sci Pollut Res 20:3639–3648CrossRefGoogle Scholar
  37. Suslick KS, Fang M, Hyeon TS (1996) Sonochemical synthesis of iron colloids. J Am Chem Soc 118:11960–11961CrossRefGoogle Scholar
  38. Tang ZH, Shen SL, Zhuang J, Wang X (2010) Noble-metal-promoted three-dimensional macroassembly of single-layered graphene oxide. Angew Chem Int Ed 49:4603–4607CrossRefGoogle Scholar
  39. Tunali S, Akar T (2006) Zn(II) biosorption properties of Botrytis cinerea biomass. J Hazard Mater 131:137–145CrossRefGoogle Scholar
  40. Vilardi G, Palma LD, Verdone N (2018a) Heavy metals adsorption by banana peels micro-powder: equilibrium modeling by non-linear models. Chin J Chem Eng 26:455–464CrossRefGoogle Scholar
  41. Vilardi G, Mpouras T, Dermatas D, Verdone N, Polydera A, Palma LD (2018b) Nanomaterials application for heavy metals recovery from polluted water: the combination of nano zero-valent iron and carbon nanotubes. Competitive adsorption non-linear modeling. Chemosphere 201:716–729CrossRefGoogle Scholar
  42. Vilardi G, Palma LD, Verdone N (2018c) On the critical use of zero valent iron nanoparticles and Fenton processes for the treatment of tannery wastewater. J Water Proc Engineer 22:109–122CrossRefGoogle Scholar
  43. Vilardi G, Ochando-Pulido JM, Stoller M, Verdone N, Palma LD (2018d) Fenton oxidation and chromium recovery from tannery wastewater by means of iron-based coated biomass as heterogeneous catalyst in fixed-bed columns. Chem Eng J 351:1–11CrossRefGoogle Scholar
  44. Vilardi G, Ochando-Pulido JM, Verdone N, Stoller M, Palma LD (2018e) On the removal of hexavalent chromium by olive stones coated by iron-based nanoparticles: equilibrium study and chromium recovery. J Clean Prod 190:200–210CrossRefGoogle Scholar
  45. Wang H, Yuan X, Wu Y, Huang H, Zeng G, Liu Y, Wang X, Lin N, Qi Y (2013) Adsorption characteristics and behaviors of graphene oxide for Zn(II) removal from aqueous solution. Appl Surf Sci 279:432–440CrossRefGoogle Scholar
  46. Wang C, Luo H, Zhang Z, Wu Y, Zhang J, Chen S (2014) Removal of As and As(V) from aqueous solutions using nanoscale zero valent iron-reduced graphite oxide modified composites. J Hazard Mater 268:124–131CrossRefGoogle Scholar
  47. Xu M, Zhu J, Su H, Dong J, Ai S, Li R (2012) Electrochemical determination of methyl parathion using poly (malachite green)/graphene nanosheets–nafion composite film-modified glassy carbon electrode. J Appl Electrochem 42:509–516CrossRefGoogle Scholar
  48. Xvéronique M, Magalie B, Alain B (2006) Cadmium and zinc bioaccumulation and metallothionein in response in two freshwater bivalves (Corbicula fluminea and Dreissena polymorpha) transplanted along a polymetallic gradient. Chemosphere 65:609–617CrossRefGoogle Scholar
  49. Yan WL, Lien H-L, Koel BE, Zhang W-X (2013) Iron nanoparticles for environmental clean-up: recent developments and future outlook. Environ Sci: Processes Impacts 15:63–77Google Scholar
  50. Yanagisawa H, Matsumoto Y, Machida M (2010) Adsorption of Zn(II) and Cd(II) ions onto magnesium and activated carbon composite in aqueous solution. Appl Surf Sci 256:1619–1623CrossRefGoogle Scholar
  51. Yin H, Zhou Y, Meng X, Shang K, Ai S (2011) One-step "green" preparation of graphene nanosheets and carbon nanospheres mixture by electrolyzing graphite rob and its application for glucose biosensing. Biosens Bioelectron 30:112–117CrossRefGoogle Scholar
  52. Zhang W-X (2003) Nanoscale iron particles for environmental remediation: an overview. J Nanopart Res 5:323–332CrossRefGoogle Scholar
  53. Zheng T, Zhan J, He J, Day C, Lu Y, McPherson GL, Piringer G, John VT (2008) Reactivity characteristics of nanoscale zerovalent iron−silica composites for trichloroethylene remediation. Environ. Sci. Technol. 42:4494–4499CrossRefGoogle Scholar
  54. Zhu J, Wei S, Gu H, Rapole SB, Wang Q, Luo Z, Haldolaarachchige N, Young DP, Guo Z (2012) One-pot synthesis of magnetic graphene nanocomposites decorated with core@double-shell nanoparticles for fast chromium removal. Environ. Sci. Technol. 46:977–985CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.State Key Laboratory for Pollution Control and Resource Reuse, College of Environmental Science and EngineeringTongji UniversityShanghaiPeople’s Republic of China
  2. 2.Department of PhysicsTongji UniversityShanghaiPeople’s Republic of China

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